Fast bases of the azole series



United States PatentfQfifice 2,695,298

Patented Nov. 23, 1954 exaniilples. Where not otherwise noted, parts are by weig t. 2,695,298 7 Example 1 FAST BASES OF THE AZOLE SERIES V QHSO Frederick Brody, New York, N. Y., and Robert S. Long, H

Bound Brook, N. J., assignors to American Cyanamid 000E Company, New York, N. Y., a corporation of Maine NE N0 Drawing. Application March 1, 1952, 10

Serial No. 274,490 o' @1130 5Claims. (Cl. 260305) V A mixture of 2.1 parts of 2,5-dimethoxy-4naminon acetanilide, 3.07 parts of 2-chlorobenzoxazo1e and Zparts This invention relates to eennnnndn of the fennnln 1e iffi3? %i$dn ;if1." ifi?mili; R0 I cooled, drowned and filtered. The product may be crystallized from ethanol.

NHR' Example 2 V GHSO R0 N NH2 1n WhlCh X is selected from the group of O and S, R is selected from the group consisting of H and RzCO and R and R2 are lower alkyl. I The production of azoic coloring matters of a greenish 0 01130 shade of blue and satisfactory fastness properties has A i t f 8,0 parts f th product of Example 1 and been a considerable problem. Such coloring matters are 120 arts of concentrated h drochloric acid in 200 arts rare and have been both expensive and frequently possess 3 p y p of ethanol is refluxed briefly, drowned, made alkaline disadvantageous. properties. We havefound that the free i h ammonia d fi1t ed Th product may b 33565 of p f lnventlon, that to 3 the crystallized from ethanol. Too long refluxing should be Pounds Where 18 hy l can be dlaZOtlZed ly avoided, since it tends to cause rupture of the oxazole and when coupled wlth aryhdes of 2-hydroxy-3-naphtho1c i i h formatign f 2 5-dimethox -p he l diacid give blue azoic coloring matters of the very rare amilm I greenish shade, coupled with good fastness character- Example 3 istics. While the rare greenish shades of blue constitute the most important azoic coloring matters which can be CHaO prepared from the dyestuifs of the present invention, the l invention is not limited thereto as a wide range of other 40 N shades may be obtained by using difierent coupling components.

While the present invention is not limited to any par- C NH OH OONHClHI ticular method of preparing the compounds, we have found that a very suitable method is the condensation of O (EH30 2-halo-benzoxazoles or -benzothiazoles with a 2,5-dialkoxy-4-aminoacyl anilide. The acylamino group can then be readily hydrolyzed to the corresponding free amines Without damaging the azole ring structure. It is Blue dyeings are obtained in the ordinary way by diazotizlng the above-prepared base with sodium nitrite and hydrochloric acid, and using the resulting diazo solution not known why the hydrolysis does not afiect the azole fg iggf i i gf z gf ggfl2 an alkahne solution of 2' ring and the invention is not intended to be limited to any theory of action. The invention is not limited to the use Example 4 of a particular dialkoxy amino acyl anilide, but acyl groups of the lower fatty acids, such as acetyl, propionyl,

etc., may be used. However, the acetanilides are available so cheaply and inexpensively that they constitute the NHCOOHI preferred raw material. The lower alkyl group represented by R may be any of the ordinary lower alkyl C-NH groups, such as methyl, ethyl, propyl, etc.

It is an advantage of the present invention that the S ,3

diazotized free bases may be used in various methods of forming azoic coloring mattem Thus, pigments may be A mixture of 17.0 parts of 2-chlorobenzoth1azole, 23.8

parts of 2,5-diethoxy-4-aminoacetanilide and 10 parts of 325:3? ik g l sgf gffig gii ggg 3 52:533 :glggg 2 hydrochloric acid in 259 parts of 50% dioxane-water fabrics and the color developed by adding the diazo comi refluxed untll 18 complete" The mlxmre pound, or stable derivatives of the diazo compound, such 15 then 9 growned parts of Water and filtered as diazoamino compounds, may be incorporated in the A goo yle 0 Product is o tamed suitable azoic printing pastes, the final color being de- Example 5 veloped by acld 1n the usual manner.

Among the ice color coupling components which may 021150 be used for this purpose are such compounds as betanaphthol, 8 amino 2 naphthol, 8 acetylamino 2 N naphthol, benzyl naphthols, pyrazolones, hydroxybenzofiuorenones and the various N-substituted amides such as arylides of 2-hydroxy-3-naphthoic acid, 2-hydroxy-3- anthroic acid, of methyl and dimethylsalicylic acids, of hydroxybenzacridone carboxylic acids, hydroxybenzofuran carboxylic acids, of hydroxybenzothiophene car- A mixture of 3.71 parts of the product of Example 4 boxylic acids, of acetoacetic acid, of benzoylacetic acid with 12 parts of concentrated hydrochloric acid and 20 and the like. parts of ethanol is refluxed until hydrolysis is complete,

This invention is further illustrated by the following drowned in parts of water and then made alkaline with sodium hydroxide. On filtration, an excellent yield of product is obtained, which may be recrystallized from ethanol.

. Example 6 (hHlO CNH AH ONHOa 10 S 021350 The product of Example 5 is diazotized in the normal way and used to develop cloth padded with Z-hydroxy- 5 3-naphthoic anilide. It gives blue dyeings of extremelv greenish shade and good fastness properties.

in which X is selected from the group consisting of O and S, R is selected from the group consisting of H and 30 R200 and R and R2 are lower alkyl.

2. A compound of the formula CHaO N NHCOOH: 35

\CNH

4 3. A compound of the formula N\ NE:

\ C-NH O CH:

4. A compound of the formula C2Ha0 /N NBC 0 0H: 0 \CNH S OZHBO 5. A compound of the formula GzHaO N NH:

\CNH

S C2Hs0 References Cited in the file of this patent Number UNITED STATES PATENTS 

1. A COMPOUND OF THE FORMULA IN WHICH X IS SELECTED FROM THE GROUP CONSISTING OF O AND S, R'' IS SELECTED FROM THE GROUP CONSISTING OF H AND R2CO AND R AND R2 ARE LOWER ALKYL. 